Chemical Vapor Deposition of Copper from Cu(I) Compounds

Hampden‐Smith, Mark J.; Kodas, Toivo T.

doi:10.1002/9783527615858.ch5

Cited by 11 publications

(4 citation statements)

References 111 publications

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“…For the case of copper CVD from precursor molecules that include hfac ligand͑s͒, it has been suggested that the rate-limiting step is the removal and/or desorption of the hfac ligand, possibly through a disproportionation process that converts two adsorbed Cu-͑hfac͒ to one Cu(hfac) 2 , that volatilizes, and a Cu that remains as the metal deposit. 17,18 Based on the results presented here, the presence of the adsorbed iodine accelerates this process. This is supported by experimental results for iodine-catalyzed copper CVD using a different ͑hfac͒Cu-based precursor, specifically ͑hfac͒Cu͑3,3-dimethyl-1-butene͒.…”

Section: Discussionmentioning

confidence: 63%

Interconnect Fabrication by Superconformal Iodine-Catalyzed Chemical Vapor Deposition of Copper

Josell

Kim²,

Wheeler

et al. 2003

J. Electrochem. Soc.

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The mechanism behind superconformal filling of fine features during surfactant catalyzed chemical vapor deposition ͑CVD͒ is described and the metrology required to predict it is identified and quantified. The impact of adsorbed iodine coverage on copper deposition rate during chemical vapor deposition of copper on planar substrates is determined first. These kinetic parameters are then used in a model based on the curvature-enhanced accelerator coverage mechanism to predict superconformal filling during iodine-catalyzed CVD. In this model, the coverage of the adsorbed catalyst is presumed to change with surface area during interface evolution. The surface area decreases along the bottoms of submicrometer dimension features, increasing the local coverage and deposition rates and thereby enabling superconformal filling. Experimental filling results are then described and shown to be consistent with the predictions.

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Section: Discussionmentioning

confidence: 63%

Interconnect Fabrication by Superconformal Iodine-Catalyzed Chemical Vapor Deposition of Copper

Josell

Kim²,

Wheeler

et al. 2003

J. Electrochem. Soc.

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“…Cu has intrinsic advantages over Al such as lower resistivity and better resistance to electromigration and stress-induced migration. Thus Cu interconnects, combined with low- k materials, offer better chip performance, higher reliability, and lower power consumption compared to Al interconnects in silicon-based semiconductors. − Current Cu film deposition technologies are either vacuum-based methods such as physical vapor deposition (PVD) and chemical vapor deposition (CVD), − or solution-based methods such as electroless deposition and electrodeposition. − Although highly pure Cu films can be deposited, Cu PVD is often considered to be unsuitable for Cu damascene process. This is because Cu PVD often results in poor gap filling and conformity and creation of a void when depositing high-aspect-ratio features .…”

Section: Introductionmentioning

confidence: 99%

Deposition of Copper Particles and Films by the Displacement of Two Immiscible Supercritical Phases and Subsequent Reaction

et al. 2009

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Copper (Cu) particles and films were produced by forming Cu(II) compound (Cu(hfac) 2 • H 2 O) films on substrates using a displacement from two immiscible supercritical phases (DISP) technique followed by reducing the copper(II) compound films in hydrogen at 200 °C. Various surfaces including native oxide of silicon (SiO x ), titanium nitride (TiN), tungsten (W), and low-k dielectric materials such as Coral, JSR5109, and Silox were used as substrates. The nucleation and growth behavior of the Cu DISP process was evaluated over a range of reduction times (from 5 to 60 min) and copper(II) compound concentrations (0.5-3 wt %). At short reduction periods (5-15 min) or low Cu(II) compound concentrations (∼ 0.5 wt %), Cu particles ranging from 60 to 95 nm in diameter were produced. In contrast, at long reduction periods (45-60 min) and high concentrations (∼3 wt %), continuous Cu films with 220-450 nm in thickness were deposited on the substrates. A morphology transition from particle to film was observed at medium reduction period (∼30 min) or medium concentration range (∼1 wt %). High affinity of TiN to Cu nucleation and film formation leads to more dense and smooth films than Cu films deposited under similar conditions on SiO x . However, nucleation of Cu DISP is not very sensitive to the surface conditions of the substrates compared with Cu CVD (chemical vapor deposition). Chemical composition analysis of the Cu film on TiN and SiO x by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) revealed that highly pure Cu films were obtained from Cu DISP.

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“…There is an extensive collection of literature on the deposition of Cu films by CVD using organometallic precursors. The most favorable precursor molecules are ligand-stabilized Cu(I) and Cu(II) β-diketonates, , which are fluorinated to increase volatility. Processes based on Cu(I) precursors generally yield higher deposition rates and do not require a carrier gas, and the lower oxidation state produces lower decomposition temperatures.…”

Section: Introductionmentioning

confidence: 99%

“…Deposition of solid Cu(0) metal from Cu(I) hexafluoroacetylacetonate precursors occurs by a thermally induced disproportionation reaction where L is a Lewis base such as a triorganophosphine, olefin, or alkyne. At surface temperatures of 150−550 °C the deposition rate is typically on the order of 0.1 μm/min − Pyrolytic laser induced CVD of a hexafluoroacetylacetonate trimethylvinylsilane Cu(II) precursor in the presence of water vapor produced high-purity Cu lines at a growth rate of 1.8 μm/min, but under anhydrous conditions the growth rate was low and large amounts of carbon were incorporated …”

Section: Introductionmentioning

confidence: 99%

Removal of Copper from Silicon Surfaces Using Hexafluoroacetylacetone (hfacH) Dissolved in Supercritical Carbon Dioxide

2005

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Copper was etched from a silicon surface using the chelator hexafluoroacetylacetone (hfacH) dissolved in supercritical carbon dioxide (scCO 2 ) at 40-60 °C and 100-250 atm. Copper was deposited on Si(100) using doped HF solutions in the form of 10-90 nm Cu islands, as shown by scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS) indicated the islands were composed of Cu(I) 2 O due to air exposure before etching was attempted. Oxidation of the Cu(I) was performed using aqueous 30% H 2 O 2 or a UV-Cl 2 gas phase, forming shells of Cu(II)O or Cu(II)Cl 2 , respectively, surrounding cores of Cu(I) 2 O. SEM images showed that the Cu(II)O had a flake morphology. The Cu(II) shells were removed selectively to the Cu(I) 2 O cores by processing with pure scCO 2 and rapidly releasing the system pressure (300 atm/min). Mechanical failure of the Cu(II)O and Cu(II)Cl 2 when CO 2 in stress corrosion cracks quickly expanded delaminated these layers, leaving only Cu(I) 2 O on the surface. Etching of both Cu(II) and Cu(I) was achieved when oxidized samples were processed in scCO 2 containing approximately 120 ppm of hfacH for 2 min. Nucleophilic attack of Cu(II) centers by hfacH formed copper(bis-hexafluoroacetylacetonate), Cu(hfac) 2 and water, or the monohydrate Cu(hfac) 2 ‚H 2 O, which was soluble in scCO 2 . The Cu(hfac) 2 ‚H 2 O byproduct is proposed to oxidize Cu(I) 2 O to Cu(II), allowing attack and etching by hfacH.

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Chemical Vapor Deposition of Copper from Cu(I) Compounds

Cited by 11 publications

References 111 publications

Interconnect Fabrication by Superconformal Iodine-Catalyzed Chemical Vapor Deposition of Copper

Interconnect Fabrication by Superconformal Iodine-Catalyzed Chemical Vapor Deposition of Copper

Deposition of Copper Particles and Films by the Displacement of Two Immiscible Supercritical Phases and Subsequent Reaction

Removal of Copper from Silicon Surfaces Using Hexafluoroacetylacetone (hfacH) Dissolved in Supercritical Carbon Dioxide

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